WO2010040725A1 - Aufwickelbarer fliesenaufbau, verfahren zur herstellung sowie die verwendung - Google Patents
Aufwickelbarer fliesenaufbau, verfahren zur herstellung sowie die verwendung Download PDFInfo
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- WO2010040725A1 WO2010040725A1 PCT/EP2009/062925 EP2009062925W WO2010040725A1 WO 2010040725 A1 WO2010040725 A1 WO 2010040725A1 EP 2009062925 W EP2009062925 W EP 2009062925W WO 2010040725 A1 WO2010040725 A1 WO 2010040725A1
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- tile
- carrier
- carrier layer
- polycarbonate
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Definitions
- the invention relates to a Jerusalemwickelbaren tile construction, a method for producing the tile construction and the use of this tile construction for the production of a tile covering. Furthermore, the invention relates to the use of organic polysilazanes in the manufacture of a rollable tile construction.
- Tiles such as ceramic tiles, are commercially available in a variety of different variations. They differ in their structure, the materials they are made of, and their properties.
- Ceramic tiles usually consist of a mixture of kaolin, feldspar, quartz and clay, which is coated with a ceramic coating, partially printed with patterns and partially provided with structures.
- a classification of the different ceramic tiles in e.g. Interior wall, floor, ceiling, kitchen, bathroom, exterior wall tiles and industrial ceramic tiles are given by the materials and manufacturing conditions used.
- non-flexible, non-coiled ceramic tiles that has become increasingly popular in recent years is those tiles which have self-cleaning, anti-soiling and / or have antimicrobial effects.
- Such ceramic tiles are advertised, for example, under the label "Hydrotect”.
- a ceramic wallcovering composite consisting of a support material and at least one ceramic coating, wherein optionally a ceramic intermediate layer may be present.
- the wallcovering assemblies of WO 2005/080684 are wallpapers which contain ceramic particles in the ceramic coating in a silicon-containing network which is linked by Si-O-Si bridges.
- the silicon-containing network of the ceramic coating is either a purely inorganic network which is formed via the oxygen bridges or else an inorganic-organic network in which the organic radicals are bonded to the silicon.
- ceramic particles are suspended in a polymeric sol which can be prepared by mixing at least one silane with an alcohol and an acid. This suspension is applied to the support material and then solidified.
- a ceramic intermediate layer is provided, which is produced by a sol-gel process, wherein the sol acts as an inorganic adhesive.
- Tile coverings in particular ceramic tile coverings and the associated FHen senaccumulated, which is flexible and windable in its entirety are not described.
- the disadvantages of sol / gel coatings are well known. Thus, the durability of sol / gel coating systems by the necessary use of acidic or alkaline catalysts is short lived. In addition, the corresponding coating systems usually do not show sufficient adhesion to the substrate.
- the concrete surface is provided with an intermediate layer of a slightly elastic material, which may contain an epoxy resin, a urethane resin and / or acrylic resin.
- This intermediate layer is coated with a surface layer of a polysilazane to obtain a sufficient hardness of the coating.
- the surface coating is designed so that when cracking the substrate made of concrete, the coating not destroyed.
- the object thus produced is neither flexible nor rollable, but rigid and thus unsuitable for the production of a Jerusalemwickelbaren tile material.
- WO 2006/108503 a method for improving the barrier properties of ceramic barrier layers is known.
- a barrier layer of ceramic material is coated with a solution of perhydropolysilazane and subsequently cured to form a silicon oxide layer.
- Plastic films, plastic films or laminates with a plastic film onto which the deposition of the ceramic barrier layer is applied are proposed as flexible carrier materials.
- barrier layers of ceramic material having a thickness of 10 nm to 200 nm, layers of Al 2 O 3 or SiO x are described.
- US-A-2553314 describes a method to make the surfaces of materials water repellent.
- liquid methylsiliconamine compounds are applied to surfaces such as paper, cotton, wool, ceramic bodies, aluminum, etc. introduced.
- organic polysilazanes as a surface coating for tile structures for the production of tile coverings is not described.
- the specific requirements of tiles such as hardness, abrasion resistance, acid resistance and stain sensitivity are not discussed, nor are any specific layer combinations for the manufacture of tile structures.
- US-A-6383642 describes transparent support materials having a hydrophobic or oleophobic coating formed by plasma CVD. Silicon compounds such as silanes, alkoxysilanes, fluorosilanes, siloxanes or silazanes are deposited in the vapor phase on a carrier material to form a surface coating in order to achieve a dirt and water resistance on a variety of surfaces, such as furniture, doors, glass ceramic plates, bathtubs and water basins. Layer structures, as described according to the invention for producing a windable tile structure, are not disclosed. On the special properties of tile structures such as the required hardness, acid resistance, stain resistance, abrasion resistance, etc. is also not discussed for this reason.
- US-A-6080455 discloses protective shells for radomes for rockets in which a titania-containing polysiloxane layer is over-coated as a coating of a quartz cladding impregnated with a resin.
- a titania-containing polysiloxane layer is over-coated as a coating of a quartz cladding impregnated with a resin.
- the use of polysilazanes in the manufacture of flexible rollable tile structures is not described.
- a coating agent with UV-protecting and water-repellent properties is known, which can be used, for example, for rubber products. It is an amine radical-containing polysilazane formulation. The use of polysilazane surface layers in the manufacture of tile structures is not suggested hereby. It is obvious that rubber products have to have completely different properties than tile structures.
- protective coatings for documents such as credit cards, identity cards and other plastic cards are known. Textile materials, paper and / or plastic materials are provided with a protective coating containing ceramic materials as well as silanes and / or silazanes.
- the requirements for protective coating for documents on the one hand and on the document materials on the other hand are of a completely different nature than the requirements that have to be placed on materials for tile structures, in particular as regards the hardness, acid resistance, abrasion resistance and so on.
- Another essential difference lies in the combinations of individual layer materials for producing a rollable tile structure, which are not suggested by WO 03/106190.
- WO 2005/068181 describes photocatalytic particles for floor laminates, the laminate containing binder materials selectable from a wide variety of compositions including, for example, melamine resins, polyester resins, polyurethane resins, polysilane resins, polysiloxane resins, silazane resins, acrylamide resins, acrylic urethane resins and polyacrylamide resins, just a few to name.
- the laminate comprises a decorative outer layer optionally having a protective layer and a base layer, the decorative upper layer comprising a network of fibers in which the photocatalytically active particles are embedded in a binder.
- Cellulose fibers are used as fiber materials, for example compounds such as titanium dioxide, iron (III) oxide, zinc oxide, etc., as photocatalytically active particles.
- organic polysilazanes in the production of rollable tile structures is not included or suggested by this document.
- the object of the present invention is therefore to provide tile structures, in particular ceramic tile structures, which can be wound up, can be easily assembled and handled, and have good scratch resistance, washability, chemical resistance and long-term stability. Furthermore, a method for producing these tile structures is to be provided.
- a tile construction according to claim 1 wherein a carrier layer and a surface layer are connected to each other and the surface layer has a cured organic polysilazane network, wherein the tile construction is designed to be wound up.
- Fig. 1 shows a cross section of a windable tile structure with connection to the substrate according to a preferred embodiment of the present invention which, from the outer surface to the inside, has the following structure: - Surface layer (2) of hardened organic Polvsilazanen - first carrier layer (I)
- FIG. 2 shows a cross section of a windable tile construction with connection to the substrate according to a preferred embodiment of the present invention which, from the outside surface to the inside of the
- Underground has the following structure:
- Fig. 3 shows a cross section of a windable tile structure with connection to the ground according to a preferred embodiment of the present invention which, from the outer surface to the inside, has the following structure: - Surface layer (2) of hardened organic Polvsilazanen
- FIG. 4 shows a cross section of a windable tile construction with connection to the substrate according to a preferred embodiment of the present invention, which, from the outside surface inwards towards the ground, has the following construction:
- FIG. 5 shows a cross section of a windable tile structure with connection to the ground according to a preferred embodiment of the present invention which, from the outside surface to the inside, has the following structure: - Surface layer (2) of hardened organic Polvsilazanen
- FIG. 6 shows a cross-section of a windable tile construction with connection to the substrate according to a preferred embodiment of the present invention, which, from the outside surface to the inside, has the following structure:
- FIG. 7 shows a cross section of a windable tile structure with connection to the substrate according to a further preferred embodiment of the present invention, which, from the outside surface to the inside, has the following structure: surface layer (2) of organic polysilazane (seal) first carrier layer of polycarbonate (carrier layer (I)) decorative layer (4) second carrier layer of nonwoven (carrier layer (5)) adhesive for connection to the substrate substrate
- FIG. 8 shows a cross section of a windable tile construction with connection to the substrate according to a further preferred embodiment of the present invention, which, from the outside surface inwards towards the ground, has the following structure:
- FIG. 9 shows a cross-section of a windable tile structure with connection to the substrate according to a further preferred embodiment of the present invention, which, from the outside surface to the inside, has the following construction and sound insulating properties: - surface layer (2) with organic polysilazane network
- Nano ceramic layer (3) consists of SiOx carrier layer (1) of flexible polyolefin (Sarnafil ®)
- FIG. 10 shows a cross section of a windable tile construction with connection to the substrate according to a further preferred embodiment of the present invention, which, from the outside surface inwards toward the ground, has the following construction and a metallic appearance:
- Nanoceramic layer (3) made of SiOx decorative layer (4)
- Support layer (1) made of aluminum
- the object of the present invention is therefore to provide a rollable tile construction, i. a tile composite material, wherein the structure of the tile composite material is multi-layered.
- a windable tile construction is provided, which is the basis for all other tile structures according to the invention.
- the tile construction according to the first preferred exemplary embodiment according to FIG. 1 comprises a carrier layer 1 and a surface layer 2. Both the carrier layer 1 and the surface layer 2 are flexible and thus windable, and the connection of both layers also results flexible and windable construction.
- the term "flexible and windable” means in this case that the tile construction is not rigid, but flexible both in the longitudinal and in the transverse direction and on a roll or drum is designed to be wound. This makes it possible to provide the tile construction according to the invention in a wound-up form in a user-friendly manner.
- the terms “rollable” and “rollable” are used interchangeably as synonyms.
- the radii for the delivery of the rollable, ie windable tiles according to the invention are 5-50 cm, in particular 10-30 cm, particularly preferably 15-25 cm. When laying narrowest radii of at least 2 cm, in particular 3 cm, more preferably 5 cm are possible.
- the individual layers of the tile composite material are more flexible and can be rolled up with a smaller radius than the overall composite, which the rollable tile forms.
- the tile construction according to the invention is also referred to in its entirety as a "rollable or windable tile".
- the carrier layer 1 is a rollable, i. A windable material which may consist of a polymer, a ceramic, a metal, glass or cellulose or composites of these materials or of composite materials with these materials together with other materials or which contains these materials. It is important that the carrier layer is flexible and rollable and that a surface layer 2 can be applied to this carrier layer.
- the surface layer 2 can be connected either directly to the carrier layer 1 or via intermediate layers with the carrier layer.
- the carrier layer 1 consists of a metal or contains a metal-containing material
- the metals used are preferably aluminum, such as aluminum foil or thin strip, copper, chromium, nickel, zinc, titanium, vanadium, magnesium, iron and / or steel. Also usable are chemical compounds and alloys of or with these metals as well as combinations of these metals. Particular preference is given to using support layers of aluminum in order to obtain a metallic appearance of the surface.
- the thickness of the metallic layer is e.g. about 20-500 microns, preferably about 100-150 microns.
- the carrier layer 1 may also consist of a polymer material. All flexible and rollable polymer materials or composites with polymeric materials can be used. Particular preference is given to support materials made of polycarbonate, Polymethyl methacrylate, polyether ketone, polyamide, polyethylene terephthalate, polyvinyl chloride, polyolefins, polyethylene, polypropylene, oriented polypropylene, polyester and polystyrene. In the polyolefins in particular materials with or made of flexible polyolefins are used. These materials are also known as thermoplastic polyolefin or flexible polyolefin alloy. The basis of such flexible poly olefins are polyethylene and polypropylene materials.
- Polycarbonates are furthermore particularly preferably used as polymeric carrier layer materials.
- Polycarbonates are polymers of the family of polyesters belonging to the prior art and offered under various trade names.
- Such polycarbonate carrier materials are offered in the form of polycarbonate films, for example from Bayer MaterialScience under the brand names Makrofol®, Bayfol® or Marnoth®. Of course, other known per se polycarbonate films of different polycarbonate materials and their mixtures can be used.
- such polycarbonates are used which are highly transparent. However, it is possible to use colored polycarbonates or matt or semitransparent polycarbonates. These possible variations represent a not to be underestimated advantage of the invention flow structure.
- the support material may optionally be backed and reinforced with a non-woven 5, as shown for example in FIGS. 6 and 7, which equalizes the unevenness in the substrate on which the tile construction is applied and a simpler application of the adhesive and better adhesion the underground allows.
- a non-woven 5 Between the carrier layers 1 and 5, one or more further layers, for example a decorative layer 4, can be arranged.
- Nonwoven materials are textile fabrics made of individual fibers. As an alternative to nonwoven materials, fabrics and films can also be used become. Nonwoven materials are all nonwovens known per se, ie, for example, those of animal or vegetable origin. However, fiber materials made of chemical fibers such as polypropylene, polyethylene, polyvinyl chloride, polyesters such as polyethylene terephthalate are particularly preferred.
- mineral fiber materials are those of glass, mineral wool and basalt. Particular preference is given to using nonwovens which have soundproofing and / or heat-insulating properties which consist of fire-retardant materials or contain flame-retarding additives and which ensure a good bond to the substrate.
- the connection of the nonwoven materials with the carrier materials can be carried out by methods known per se, such as, for example, dry or wet laminating or by pressing with or without adhesive.
- the thickness of the carrier material is basically not critical.
- a carrier material of such thickness is selected that the carrier material has a sufficiently high rigidity with simultaneous flexibility and rollability. It is crucial that the thickness is designed so that the tile structure provided according to the invention, in particular the ceramic tile construction, also remains rollable.
- the support layers formed from the support materials preferably each have a thickness in the range of 100 to 200 ⁇ m, e.g. 120 - 170 ⁇ m; the total thickness of the tile construction is in a range of 300-1000 ⁇ m, preferably 400-600 ⁇ m or 300-500 ⁇ m.
- the tile structure may contain various carrier layers, which may consist of the same or of different materials.
- a carrier layer 1 made of polycarbonate can be combined with a carrier layer 5 made of aluminum, which are optionally connected to one another directly or via an intermediate layer 3, which may be a nanoceramic layer.
- the tile composite can also contain a third carrier layer, wherein the number of layers is limited by the requirement of the rollability of the entire tile structure.
- the radii to be complied with have been described above.
- the support layer pointing inwards to the substrate can preferably be deposited, as stated above, with a nonwoven material which then forms the second or third carrier layer.
- a decorative or design layer 4 can be applied.
- the decorative layer can also be applied to the underside of the carrier material.
- the application of the decorative layer on the substrate can be done by methods known per se. Examples include printing processes such as flexographic printing or digital printing.
- the decorative layer may also be part of the backed fleece used for reinforcing the carrier material, or, if no fleece is used, the carrier material may be deposited with the decorative layer.
- the decorative layer can be produced as a single layer and bonded to the carrier material or the carrier materials using the customary termination methods, for example by adhesives or by adhesion forces.
- the carrier material can be printed with the decorative layer.
- the support materials can also be directly bonded together, i. the first carrier layer with the second carrier layer or the second carrier layer with the third carrier layer.
- An example of this is the connection of an aluminum carrier as a second carrier layer with a nonwoven material as the third carrier layer.
- the person skilled in the art can combine the carrier materials with one another in order to contain the desired properties of the end product with this variety of possible variations.
- the tile structures according to the invention are characterized by the material properties which result from the sum of the properties of the carrier layers used and the surface coating.
- a particular difficulty in finding the problem solutions of the present invention was to provide a tile structure, which has the known characteristics of use of ceramic tiles and additionally meets the criteria of flexibility, a significantly lower weight compared to ceramic tiles and easier processability.
- properties of ceramic tiles include a limited water absorption capacity to make the tiles and the substrate resistant to moisture and also to frost, a high abrasion resistance, resistance to scratching, against exposure to chemicals such as acids and alkalis, especially against chemicals, as used in commercial cleaning agents a good cleaning ability to meet hygienic requirements, resistance to scratching and long-term stability.
- Polysilazanes are known per se. These are polymers of the following general structural formula (1), whose polymer chains are built up alternately from silicon and nitrogen atoms.
- R ', R ", R'” independently of one another represent hydrogen or an optionally substituted alkyl, aryl, vinyl or (trialkoxysilyl) alkyl radical, with the proviso that not all radicals R ', R “and R' "are simultaneously hydrogen, wherein n is an integer and n is such that the polysilazane has a number average molecular weight of 150 to 150,000 g / mol.
- organic polysilazanes which can be used according to the invention for coating the windable carrier composite material preferably comprise a solution of an organic polysilazane or a mixture of organic polysilazanes of the general formula (2),
- R ', R "' and R * * * are hydrogen and R", R * and R * * are methyl; R ', R "' and R * * * are hydrogen and R", R * is methyl and R * * is vinyl; - R ', R'", R * and R *** are hydrogen and R" and R ** are methyl.
- n and p are such that the organic polysilazane has a number average molecular weight of 150 to 150,000 g / mol.
- R ', R' "and R ** * are hydrogen and R", R *, R ** and R2 are methyl, R3 is (triethoxysilyl) propyl and Rl is methyl or hydrogen.
- n, p and q are such that the polysilazane has a number average molecular weight of 150 to 150,000 g / mol.
- the proportion of polysilazane in the solvent is from 1 to 80% by weight of polysilazane, preferably from 5 to 50% by weight, particularly preferably from 10 to 40% by weight.
- organic content in the polysilazane structure and the reduced Si-H content in the binder Due to the organic content in the polysilazane structure and the reduced Si-H content in the binder, flexible structures are obtained. These systems are particularly suitable for coating the rollable carrier materials (1) or flexible nanoceramic layers (2), since they have a higher coefficient of thermal expansion.
- Particularly suitable solvents for the polysilazane formulation are organic solvents which contain no water and no reactive groups (such as hydroxyl or amine groups).
- aliphatic or aromatic hydrocarbons such as aliphatic or aromatic hydrocarbons, halogenated hydrocarbons, esters such as ethyl acetate or butyl acetate, ketones such as acetone or methyl ethyl ketone, ethers such as tetrahydrofuran or dibutyl ether, and mono- and polyalkylene glycol dialkyl ethers (glymes) or mixtures of these solvents.
- An additional constituent of the polysilazane formulation may be further binders such as are commonly used for the production of paints.
- binders such as are commonly used for the production of paints.
- These may be, for example, cellulose ethers and esters, such as ethylcellulose, nitrocellulose, cellulose acetate or cellulose acetobutyrate, natural resins such as rubber or rosin resins or synthetic resins, such as polymerization or condensation resins, for example aminoplasts, in particular urea and melamine-formaldehyde resins, alkyd resins, acrylic resins, polyesters or modified Polyester, epoxies, polyisocyanates or blocked polyisocyanates or polysiloxanes act.
- ingredients of the polysilazane formulation may include additives, e.g. Viscosity of the formulation, background wetting, film formation, sliding action or the Ablmont behave, which are described in more detail below.
- Additional constituents of the polysilazane formulation may be catalysts such as, for example, organic amines, acids and also metals or metal salts or mixtures of these compounds.
- Catalysts are preferably used in amounts of 0.001 to 10%, in particular 0.01 to 6%, particularly preferably 0.1 to 3%, based on the weight of the polysilazane.
- amine catalysts are ammonia, methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, n-propylamine, isopropylamine, di-n-propylamine, di-isopropylamine, tri-n-propylamine, n-butylamine, isobutylamine, di-aminopropylamine.
- organic acids examples include acetic acid, propionic acid, butyric acid, valeric acid, caproic acid.
- metals and metal compounds as catalysts are palladium, palladium acetate, palladium acetylacetonate, palladium propionate, nickel, nickel acetylacetonate, silver powder, silver acetylacetonate, platinum, platinum acetylacetonate, ruthenium, ruthenium macetylacetonate, ruthenium carbonyls, gold, copper, copper acetylacetonate, aluminum macetylacetonate, aluminum tris ( ethyl acetoacetate).
- the presence of moisture or oxygen may play a role in the cure of the coating.
- the rapid curing at high or low humidity or at high or low oxygen content can be achieved.
- the person skilled in these influences are known and he will adjust the atmospheric conditions by appropriate optimization methods.
- the polysilazane formulations used in accordance with the invention can be applied to all windable carrier materials and flexible nanoceramic layers used in the present invention.
- the polysilazane lacquer can be applied directly to the wound-up carrier material as well as to the flexible nanokeramic layer. Due to the smoothing properties and the favorable surface polarity, a high-gloss, easy-to-clean surface is achieved in each case.
- Coating with the polysilazane formulation can be accomplished by methods commonly used in the paint industry. These may be, for example, spraying, diving or flooding. Subsequently, a thermal aftertreatment can take place in order to accelerate the curing of the coating.
- the curing takes place already at room temperature, but can be accelerated by heating.
- the gloss level increases compared with the uncoated material.
- the hardening of the coating takes place at room temperature and below due to the high reactivity of the polysilazane, but can be accelerated by raising the temperature.
- the coating is preferably cured at a temperature in the range from 10 to 120 ° C., preferably from 80 to 100 ° C.
- the maximum possible temperature for curing depends on the windable carrier material 1, to which the coating is applied. In the case of metals, such as aluminum, this may be higher temperatures of 180 to 200 ° C. or higher. If the coating is applied to a polymer as a windable carrier material, it is advisable to work at a lower temperature so that the polymer does not soften, preferably at 25 to 120 ° C., more preferably at 80 to 100 ° C. the windable carrier material to work at 160-170 0 to C, so curing takes place within 15 - 30 min.
- the humidity has an influence on the curing of the coating.
- a faster curing takes place, which can be part of; conversely, curing in a low humidity atmosphere, such as in a drying cabinet, provides a slow and even hardening process. Therefore, the curing of the coating according to the invention can be carried out at a relative humidity of 0 to 100%.
- the flexible polysilazane coating 2 has a thickness of at least 1 .mu.m, preferably 2 to 20 .mu.m, more preferably 3 to 10 .mu.m and ensures excellent protection of the surfaces against corrosion and scratching. With such coated, wound-on carrier materials, contamination of impurities is prevented since it is a high-temperature-resistant topcoat. The cleaning is greatly facilitated due to the smooth surface.
- tile structures according to the invention in which at least one layer contains ceramic materials or consists of ceramic materials.
- a nanoceramic layer preferably of SiO x
- tile construction in the invention hereby obtains in its entirety properties which are comparable to those of a ceramic tile, for example with regard to hardness, long-term stability, acid resistance, etc., the flexibility and thus windability of the tile construction is maintained at the same time.
- ceramic tile construction is particularly due to the fact that the organic polysilazane coating of the surface layer cures, which has all the surface properties possessed by a ceramic tile according to the prior art, but at the same time does not adversely affect the windability of the entire tile structure.
- a polysiloxane structure with a higher crosslinked polysilazane structure results.
- the proportion of more highly crosslinked polysilazane structure increases towards the substrate.
- the rollable tile structure provided according to the invention consists of a carrier layer 1 with a surface layer 2 which comprises a hardened organic polysilazane network. has.
- a surface layer 2 which comprises a hardened organic polysilazane network. has.
- the properties of the inventive tile construction can be changed and adapted to the requirements of the customer and the substrate. A variety of configurations are possible, and some particularly preferred tile structures will be described in more detail below.
- FIG. 3 shows such a construction with an additional decorative layer.
- a nanoceramic layer 3 is arranged between the carrier layer 1 and the surface layer 2, that is to say the polysilazane sealing layer rests on the nanoceramic layer 3, which in turn is connected to the carrier layer 1.
- FIG. 3 An example of this is FIG. 3.
- the nanoceramic layer 3 which of course must be flexible in order to impart flexibility and rollability to the overall structure, particular preference is given to silicon oxide (SiOx) coatings which have high light transparency with outstanding barrier properties to gases and odors.
- SiOx silicon oxide
- This flexible nano-ceramic layer 3 increases the resistance of the tile structure against the ingress of water molecules, improves the kink resistance and allows high adhesion of both the polysilazane coating and the underlying windable substrates. Due to its transparency, the nano-ceramic layer 3 is suitable for making underlying decorative layers visible to the viewer.
- Such nanoceramic layers with barrier properties are commercially available under the brand CERAMIS® from Alcan Packaging.
- the SiO x layers particularly preferably used as nanoceramic layer 3 are applied to the carrier material by methods known per se, for example by electron beam evaporation of SiO 2 in vacuo. In addition to such Vakuumbedampfung a plasma polymerization is possible.
- functional components can be introduced, for example, coloring pigments such as TiO 2 in an amount which causes an effective coloring.
- the nanoceramic layer 3 can also be printed in one or more colors, for example by flexographic printing or digital printing methods. ... please note that the nanoceramic layer is exclusively SiOx Layers are revealed. If you know other nanoceramic layers, these should be included.
- the layer thickness of the flexible nanoceramic layer is preferably at least 1 ⁇ m, in particular between 3 and 15 ⁇ m, particularly preferably between 5 and 10 ⁇ m.
- barrier layers such as those of aluminum or aluminum oxide, either instead of SiO x - layers or in combination with these, can be used.
- polycarbonate or a flexible polyolefin material is preferably used as the carrier material.
- Flexible polyolefin materials are e.g. available from SIKA under the name Sarnafil®.
- Polycarbonate carrier materials are preferred layer materials due to their good optical and mechanical properties.
- the carrier layers referred to herein as "polycarbonate” may consist of polycarbonates, of polycarbonate blends, and blends of polycarbonates with other polymers.
- Such polycarbonate carrier materials are offered in the form of polycarbonate films, for example from Bayer MaterialScience, under the brand names Makrofol®, Bayfol® or Marnoth®. Of course, it is also possible to use other polycarbonate films known per se from various polycarbonate materials and their mixtures. Preference is given to using those polycarbonates which are highly transparent.
- one or more further carrier materials can be used in order to further improve the properties of the rollable or windable ceramic tile according to the invention.
- These include aluminum substrates or nonwoven web substrates (see Figures 6, 7 and 10) or other materials.
- the desired material properties can be provided by the various possible combinations of the layers.
- a prerequisite for this is always that a surface layer of an organic polysilazane network is used in conjunction with at least one flexible carrier layer.
- a first carrier layer 1 made of polycarbonate is coated with a surface layer 2 of an organic polysilazane.
- a nanoceramic layer 3 is provided, which is designed as a SiO x layer. Due to the transparency of both the polycarbonate carrier material and the nanoceramic layer 3, a decorative layer 4 is applied to the side of the nanoceramic layer 3 facing away from the carrier material made of polycarbonate.
- the decorative layer can be deposited with a further support material made of aluminum, or even with nonwoven material.
- the support material may be deposited from aluminum with a nonwoven material. An example of this is shown in FIG. 1.
- Decorative three-dimensional effects can also be achieved by applying the polysilazane coating to the tile structure or parts of the tile structure such as individual carrier layers or combinations of carrier layers, for example a combination of nanoceramic layer 3 and carrier layer 1 or a combination of carrier layer 1 and Carrier layer 5, optionally with a nanoceramic layer 3, is structured by an embossing pressure. Subsequent to the structuring, the polysilazane surface coating is applied.
- the rollable carrier material 1 for example made of polycarbonate
- the flexible nanoceramic layer 3 on the front side.
- a decorative layer 4 with design elements for example by digital printing, anodizing, screen printing, contra-printing or painting, can be applied.
- the flexible polysilazane coating is applied and cured via a roll-to-roll process.
- a roll-to-roll process is a process in which the carrier material is unrolled on a roll, one or more layers are applied in a continuous process. and the intermediate or end product thus obtained is wound up on another roll. In this manufacturing process, the final product already exists in the form of a roll during the manufacturing process.
- the carrier material 1 can be connected to further carrier materials, for example a carrier material 5 made of aluminum. This results in greater stability and higher barrier properties.
- the thickness of the nonwoven layer is about 100-1000 ⁇ m, preferably about 300-500 ⁇ m.
- the invention rollable or windable tile adapts to the ground, especially if a fleece is provided on the bottom.
- any remaining spaces between two tile tracks are grouted with the organic polysilazanes or other polysilazane materials used in accordance with the invention, ie connected to one another and sealed to the ground.
- the connection of the individual layers takes place in a manner known per se.
- the connection of the aluminum support with a nonwoven is carried out by thermal lamination at about 130 ° C.; the SiOx layer is applied in vacuo; applying the polysilazane layer by spraying or dipping.
- the roll-up or rollable tile structure provided according to the invention, in particular a tile construction with carrier layers with ceramic layers, has the following properties:
- the invention will be illustrated by means of exemplary embodiments. The following tests were used to determine and compare product properties. Scratch resistance: determined according to EN 259-1. The specimen was scrubbed 300 times. It started with a soft abrasive. Then harder agents were used gradually until the sample had a visible change in surface area. Soft, medium and hard Scotch-Brite® sponges, soft and hard brushes, steel wool and P240 grit sandpaper were preferably used.
- the tile constructions according to the invention are highly scratch-resistant and abrasion-resistant according to EN 259-1.
- Acid and stain neutrality determined according to EN 423. Pipettes, wattering ponds, chemical substances, microfibre cloths, brushes and abrasives were preferably used for cleaning. The specimen was sprinkled with ImI to 2 ml of the chemical substance. If this ran away, a Watterondelle was hung up. The main impact duration was 2h. Before each cleaning, the still wet spots were blotted with cotton, starting from the edge starting to the middle of the patch. After cleaning, the remaining spots were observed from a distance of about 800 mm at an observation angle of about 45 ° and with slow rotation of the observation table from all directions. If a stain was visible, it was rubbed off with a light abrasive or detergent and retested. The recommended tile structures are acid and stain neutral according to EN 423.
- Shock resistance determined according to EN 259-2.
- 1 joule of energy was applied at an angle of 30 degrees to the specimen, with the impactor having a diameter of 20mm and a roundness of 2mm.
- the test piece was examined with the naked eye after the fall load. It was checked whether the cover layer is intact or has irreversible damage; this is generally indicated by breaking or tearing of the surface layer, which may extend to the base of the wallcovering.
- the tile constructions according to the invention are impact resistant according to EN 259-2.
- the electron beam evaporation is used to achieve a controlled and uniform evaporation of the coating material and a high transparency.
- the layer thickness is about 8 microns.
- the side of the carrier layer facing away from the silicon oxide layer is printed with a digital printing method.
- the equipment required for this purpose are offered for example by the company Muller Martini Druckmaschinen GmbH, Maulburg.
- the printed with a decor page with a nonwoven material is laminated.
- a layer of organic polysilazanes is applied on the outside of the polycarbonate layer.
- a 40% solution of the organic polysilazane described by formula (3) in n-butyl acetate is used, which has been correspondingly additized. After the application is cured at 120 0 C within 1 h.
- the tile composite material produced in this way can be applied to the substrate, in particular walls or floors, by adhesives known per se.
- adhesives for example, adhesives from SIKA, Switzerland, are used.
- Adhesives from SIKA, and of course also adhesives and sealing materials from other companies, can also be used for the sealing of seals and transitions.
- test instruments were used: pipettes, wattered cells, chemical substances, microfibre cloths, brushes and abrasives.
- the specimens were sprinkled with ImI to 2 ml of the chemical substance. If this ran away, a Watterondelle was launched. The main impact duration was 2h.
- the still wet spots are blotted with cotton, starting from the edge starting to the center of the patch.
- the remaining spots are observed from a distance of approximately 800 mm at an observation angle of approximately 45 ° and with slow rotation of the observation table from all directions. If a stain was visible, it was rubbed off with a mild abrasive or a commercially available detergent and retested.
- test specimens used were: Vaporex vapor barrier for wet cells, Erfurt rough fiber wallpaper, Kertala, conventional tile.
- the result is shown in Table 1.
- the product according to the invention is marked as Kertala®.
- the test report states: All tested substances can simply be wiped off with a cloth and a little water. Liquids bead off strongly. There are drops forming; Kertala® will not get wet. "
- the specimen is scrubbed 300 times. It starts with a soft abrasive. Then gradually harder agents are used until the sample has a visible change in the surface.
- test specimens used were: Erfurt Raufasertapete, Vaporex ® vapor barrier, Tile, Kertala®
- the impact element had a diameter of 20 mm and a roundness of 2 mm.
- test piece was examined with the naked eye after the fall load. It was checked if the topcoat is intact, or if it has irreversible damage having. This is generally indicated by breaking or tearing of the surface layer, which may extend to the backing of the wallcovering.
- KERT ALA ® is shockproof. Depending on the carrier, the effects of shock tests were different: a hard KERT ALA ® did not result in plastic deformations, but quickly damage the glaze; soft KER-TALA led rather to a plastic deformation, but the glaze remained intact. Elastic KERTALA, which did not undergo any plastic deformation and remained intact, has proven most effective.
- a 0.030 mm thick backing film made of non-soft annealed aluminum is on the back with a nonwoven material from Erfurt, which is available under the brand name Vario Vlies®, laminated.
- the fleece is a smooth material consisting of pulp and textile fibers combined with polymeric binders.
- the aluminum foil has barrier properties to prevent the passage of water molecules.
- a ceramic silicon oxide coating is applied by electron beam evaporation.
- An organic polysilazane layer as described in Example 1 is applied to the silicon oxide layer obtained in this way.
- the tile structure obtained in this way can be connected to the substrate using adhesives known per se.
- the tile structures produced in accordance with the invention can be produced in roll form and, similar to wallpapers, can be applied to the substrate.
- the substrate can be pretreated, in particular to smooth out unevenness, for example by applying a high viscosity leveling agent or by attaching a nonwoven material either directly to the substrate or by using a tile construction comprising a nonwoven material on the side facing away from the polysilazane surface layer ,
- the substrate is pretreated with commercially available adhesives compatible with the rollable tile construction material, or the adhesive is applied directly to the polysilazane layer facing surface of the tile structure.
- the rollable tile composite materials according to the invention are cut to the appropriate length and placed side by side, track by rail.
- the joints usually produced when laying ceramic tiles are reduced to an absolute minimum, as is commonly known from wallpaper.
- the tileworks are applied to the substrate in shock-to-impact fashion and can be joined together by means of sealing materials known per se, for example from organic polysilazanes, so that a maximum surface seal is created. In this way, the subsoil is also completely sealed off against shocks against the ingress of liquids and gases from the outside.
- the surfaces obtained by applying the tile composite materials according to the invention are easy to clean. Liquid contaminants can be removed by simply wiping with a cloth, since the liquid can not penetrate the tile structure due to the polysilazane surface seal. Solid stains can also be removed by simply wiping with a cloth. More stubborn solid contaminants can be easily washed off with household-standard, in particular environmentally friendly cleaning agents, for example also dishwashing detergents. The above test results show the excellent cleaning properties of the inventive tile composites.
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- Engineering & Computer Science (AREA)
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Abstract
Description
Claims
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
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JP2011530465A JP2012505090A (ja) | 2008-10-10 | 2009-10-06 | 巻き取り可能なタイル構造体,該タイル構造体の製造方法,及びタイル被覆の構築のための該タイル構造体の使用 |
CN2009801400920A CN102177014A (zh) | 2008-10-10 | 2009-10-06 | 可卷绕的砖结构体、制备方法及应用 |
US13/121,101 US20120009400A1 (en) | 2008-10-10 | 2009-10-06 | Windable tile design, method for manufacturing and use |
RU2011138083/05A RU2011138083A (ru) | 2008-10-10 | 2009-10-06 | Структура плитки, сворачиваемой в рулон, способ производства этой структуры плитки и использование этой структуры плитки в производстве плиточного покрытия |
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EP20080166341 EP2174780B8 (de) | 2008-10-10 | 2008-10-10 | Aufwickelbarer Fliesenaufbau, Verfahren zur Herstellung sowie die Verwendung |
EP08166341.1 | 2008-10-10 |
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US (1) | US20120009400A1 (de) |
EP (1) | EP2174780B8 (de) |
JP (1) | JP2012505090A (de) |
CN (1) | CN102177014A (de) |
AT (1) | ATE552105T1 (de) |
RU (1) | RU2011138083A (de) |
WO (1) | WO2010040725A1 (de) |
Cited By (1)
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RU2612765C2 (ru) * | 2013-01-29 | 2017-03-13 | Шлюмбергер Текнолоджи Б.В. | Способ улучшения закупоривания волокнами |
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EP2426289A1 (de) * | 2010-07-12 | 2012-03-07 | Christian Kadler | Plattenförmige Wandverkleidung |
US8978536B2 (en) * | 2012-04-30 | 2015-03-17 | Future Force Innovation, Inc. | Material for providing blast and projectile impact protection |
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CN110050016A (zh) * | 2016-12-02 | 2019-07-23 | 默克专利股份有限公司 | 由可交联聚合物组合物制备光电装置的方法 |
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2009
- 2009-10-06 JP JP2011530465A patent/JP2012505090A/ja not_active Withdrawn
- 2009-10-06 US US13/121,101 patent/US20120009400A1/en not_active Abandoned
- 2009-10-06 RU RU2011138083/05A patent/RU2011138083A/ru not_active Application Discontinuation
- 2009-10-06 CN CN2009801400920A patent/CN102177014A/zh active Pending
- 2009-10-06 WO PCT/EP2009/062925 patent/WO2010040725A1/de active Application Filing
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DE202004006531U1 (de) * | 2004-04-22 | 2004-07-29 | Tillmann, Rolf | Bodenbelag |
WO2007082661A1 (de) * | 2006-01-13 | 2007-07-26 | Wkp Württembergische Kunststoffplattenwerke Gmbh & Co. Kg | Flexibler bodenbelag |
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Also Published As
Publication number | Publication date |
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CN102177014A (zh) | 2011-09-07 |
EP2174780A1 (de) | 2010-04-14 |
US20120009400A1 (en) | 2012-01-12 |
EP2174780B1 (de) | 2012-04-04 |
ATE552105T1 (de) | 2012-04-15 |
JP2012505090A (ja) | 2012-03-01 |
EP2174780B8 (de) | 2012-05-16 |
RU2011138083A (ru) | 2013-03-27 |
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